Resinous esterification products of inner ethers and methods of making same



Patented 0.1.25, 1938 Y I e amet UNITED STATES PATENT OFFICE RESINOUS ESTERIFICATION PRODUCTS OF INNER ETHERS AND METHODS OF MAK- ING SAME Kenneth R. Brown, Tamaqua, Pa., assignor to Atlas Powder-Company, Wilmington, Del., a

corporation of Delaware No Drawing." Application Mal-en 11, 1938, Serial No. 195,380

21 Claims; (01. 260-8) .fI his invention relates to a new type of synmay contain such non-functional substituents as thetic resin,and to the method of makingthe are compatible with the ring formation and do same, and more particularlyit relates to a novel not prevent the resinifying esterification of the resinous material comprising the esterificationhydroxyl groups during the reaction. The nonproduct of a resinifying polycarboxylic organic functional substitution may be performed on the acid, either alone or in combination with a fatty inner ether or on the hexahydric alcohol before oil acid, i. e., an aliphatic long chain saturated or inner ether formation. In this way, the properunsaturated monobasicj acid, and an inner ether ties of the resinous esterification product may be derivable from a straight chain hexahydric alcovaried, first, by control of the number of esteriloholbyintramolecular condensation. fiable hydroxyl groups in the polyhydric inner 1o,

This application is a continuation of my prior ether and, secondly, by the character of the nonapplications, Serial Nos. 758,865, 758,866, and functional substituent.

758,867 filed December 22, 1934. The inner ethers may be defined as cyclic car- One object of my invention is to provide a ban-oxygen compounds containing one cyclic oxy- 15, synthetic resinous product of novel characterisgen per ring (known as an oxido ring) and derived tics and constitution which has wide applicability from a hexahydric alcohol by intramolecular 0011- in the industries and great utility in plastic and densation. If only one molecule of water is recoating compositions. U moved by the, intramolecular condensation, a

Other objects, including the "novel method of monoanhydro derivative containing only one car- 20, making the resinous product, will appear from a hon-oxygen ring is obtained. If the condensaconsideration of thespecification and claims. tion removes two molecules of water from the This invention contemplates the production 01" alcohol, a dianhydro compound containing two resinous materials comprising the esterification carbon-oxygen rings, which may or may not be products of a resinifying polycarboxylic organic of the condensed type, is obtained. The number acid (a polycarboxylic organic acid capable of of members in the ring and the number of oxido 25 withstanding resiniiication temperatures without rings in the i r ether which are Possible decomposition] prior to resin formatiom'and an pend upon the arrangement of the hydroxyl inner ether of astraight chain heXahydric alp in the Chain of the y o alco ol coho]. d I j ,from which the inner ether is derived. If the The resinifying polycarboxylic organic acid may yl rin car n ms through whi 30 be either aliphatic or aromatic, or a mixture of the intramolecular condensation takes place are two or more polyca'rboxylic acids of either or both separated by only one carbon atom-, i-membered classes may be employed. The anhydride may carbon-oxygen rings only are possible; if they are be used in;place of the acid and the term polyseparated by two carbon atoms, S-membered rings 5. carboxylic organic acid, as employed herein inare obtained; and if they are separated by three eludes ,the anhydride thereof. As an example of carbon atoms, then G-membered rings are formed. the aromatic polycarboxylic. acids, the use of Whether in any particular intramolecular conwhich in many instances" is to be preferred, densation a monoor di-anhydro compound is phthalic acid may be mentioned. In the case of formed depends generally upon the conditions of 40 an aliphatic polycarboxylic acid, the acid may be the reactiomancl it is possible toform dianhydro 40 saturated, or unsaturated, and may or may not compounds containing different membered carcontain hydroxyl groups. Succinic, glutaric, bun-oxygen rings, for example, a compound conadipic, suberic, azelaic, pimaric, malic, tartaric, taininga 4- and a 6-membered ring. As a result maleic, fumaric", mucic and citric acids are exof the condensation of the hexahydric alcohols,

amples of polycarboxylic aliphatic acids which a mixture of the various inner ethers may be are applicable for use. formed. d The innerether. of the straight chain hexahy- Of the hexahydric straight-chain alcohols from \dric alcohol forming the esterification product which the inner ethers arederivable, mannitol 0 with the polycarboxylic organic acid may be emand sorbitol, due to their availability, are esper ployed directly in the reaction; or advantageously cially suitable. In order that the structures of the inner ether may be formed under the condicertain of the inner ethers may be illustrated, tions of andduring the esterification reaction by some of thesewhich maybe formed from the utilizing the polyhydricalcoholas the initial mahexahydric straight-chain alcohols have been terial. The inner-ethers maybe unsubstitutedor chosen as typical. l

The 4-membered oxido ring, known as an oxidopropan ring:

CHr-CHOH-CH(CHOH)|CH|OH CHOH The 5-membered oxido ring, known as a furan ring:

CH:(OHOH)zCH(CHOB)-CH;OH

CHOH

The S-membered oxido ring, known as a pyran ring:

CH|(CHOH);/CH-CH:OH

CHOH

onon CHOH CH CH-CHzOH The dianhydro compound containing two condensed S-membered oxido rings, known as furofuran rings:

noon on on,

on, o11'ono11 It is to be understood, of course, that the structural formulae given above showing the various rings are merely by way of example, and that the ring formation may take place between any of the other non-adjacent hydroxyl-bearing carbon atoms of the alcohol. With most hexahydric alcohols, and particularly with those especially applicable for use, the inner ether containing the furan ring appears to be the main product obtained as the result of the intramolecular condensation reaction under usual conditions, although smaller amounts of the other inner ethers of both the monoand di-anhydro type may be present. The inner ethers of the various hexahydric alcohols may also be designated by names derived from the stem of the parent alcohol by adding the characteristic suiilx, itol, for the parent alcohol; "itan" for the cyclic monoanhydro derivative or inner ether; and ide for the dianhydro derivative, the dicyclic inner ether: thus, mann-itol, mann-itan, mann-ide; dulc-itol, -itan, -ide, etc. In this connection, it may be mentioned that mannide and isomannide have been used for two definite chemical individuals, but I prefer to consider the terms itan" and ide as descriptive of the classes of monoand di-anhydro ethers of polyhydric alcohols.

As pointed out, the inner ether may be employed directly in the reaction with the resinifying polycarboxylic organic acid, or the hexahydric alcohol may be used and the inner ether formed during the course of the resin-forming process. The same type of resinous product is formed in both cases, since upon saponification, an inner ether is obtained from both resins and the hexahydric alcohol cannot be regenerated in the case where it is utilized as the original reactant. As the most convenient method of obtaining the inner ethers is by internal condensation of the polyhydric alcohol, usually the intermediate step involving the preparation and separation of the inner ether is dispensed with, and the polycarboxylic organic acid is reacted directly with the polyhydric alcohol. If desired, the inner ether may be obtained from the polyhydric alcohol under any suitable dehydrating conditions, for example, by simple heating at temperatures of 140 C. or upwards. Preferably, however, the heating is carried out in the presence of a dehydrating catalyst of either a basic or acidic nature at temperatures of 140 C. and upwards. The ethers. when formed, are preferably purifled by vacuum distillation.

When the hexahydric alcohol is employed as the original reactant, the evidence points to the fact that the intramolecular condensation forming the inner ether takes place before the hydroxyl groups are esterified, but the esteriflcation may possibly take place first. If the latter does occur, however, it is to be understood that it falls within the scope of the invention and within the claims. The claims reciting the esterification of the inner ether are to be understood to include not only the use of the inner ether as the original reactant but also the use of the hexahydric alcohol from which the inner ether is formed.

The useful resinous properties of these esters derive from the fact that they are mixtures of large aggregates built up by esterifioation from much smaller polyhydroxy inner ether and polybasic acid units. In the elaboration of these large molecules, condensation takes place with the formation not only of straight chains, but also of branched chains and so-called tridimensional molecules which result from the tying together of two or more straight or branched chains by a polybasic acid link.

It is known that the reactivity, and particularly the esterifiability, of hydroxyl groups is aifected and diminished by steric hindrance, and that in general the reactivity of functional groups such as hydroxyl or carboxyl decreases with increase in the size of the molecule to which they are attached. Accordingly, the use of stoichiometric proportions of acid and hydroxyl in the production of these resinous esters does not lead to neutral, completely reacted preparations, but gives mixtures of large molecules containing uncombined hydroxyl and carboxyl groups. Also, this effect is more pronounced, the more hydroxyls, and hence the more reactive positions, in the polyhydroxylic starting material, since tri-dimensional molecules form more readily and have in their structure hydroxyls 1. impaired due tolarger amounts oruncombined ahd"'jpartially" esterified} polycarboxylic acid.

andcarboxy1s3which are inqqd a posit'fdn to react. PSO that where; tor'instance, hexahydric straight chainalcoholsare usedas starting t materiaLonly a ffractionjoi the total hydroxyl j presentds active in the resin-formingesteriflcaf tied-{1h the first place; the original six hydroxyls are diminished by two; due to the formatlodof thetetrahydric monoanhydroderivative, Intlie second place, reaction "proceeds at r such a rate andfin a manner that, under the conditions such as 'describedtln' the examples, jonly in the neighborhoodot 2 /2or thefremalnirig 4 normally esterifiable hydrox'yls can "be" reacted Increasing the prcportionfof organic acid used above this amount favorsitheformation of more pan tially esterified" phlycarboxylic "organic acid residues, and hence a :resiriousester of higher acid numberwithout increasing effectively the Inthe preferred method of manufacture where a resinof low acid number 'isdesired, the fhexahydric alcoholor the innerether and the organic acid areerhployed in proportions so that the amount of acid: is equivalent to not more than about one-half of the totarhydroxyls in the hexahydrie alcohol, hence, aboiit three carboxylfequivalents' are used. The proportionfoi 8 acid used canbe advantageously reduced to the neighborhoodof two and one-guarter carbcxyls.

1 the =reactioh, the maximumesterification of the hydroxyls is generally attainedwith the minimum amount of uncombined'andpartlally esterified polycarboxylic acid. f

If bn the otherhand, Bl resin 01 higher'acid may be increased to n'otmore .thanabout four aoid"'equiyalents per rn'ol of inner ether. If ratiosgreater thah about'4 acidequivalents are employed, the utility of the jresinous product is These carbo'xyls are distributedibetween uncom bined a ds and the free carboi'iylsof"thepartl ally" esterijfled polycarboxylic i acid residues, both of whichficontribute.toithe high acid number. The

Y higher .thefem'ount. or acid employed ver the combining ratiospointedjout above, the higher will be the" acid number" of the resin 'duenot only to theincrea se, in the amo unt of excess unreacted acid but alsoto the" larger amount of partially esterified polycarboxfylic acid residues present; Under certain circumstances, wemay purposely I l 1 react even less than the optimum amount,-oi1acid to obtain materialfhaving averylow' acid number and somewhat different solvent properties than the typical esterification product, oritoreduce j l: to 'a minimum theproportion of an expensive ingredient. r V60 1 The proportions of the components used" thus; be regulated according to .therequirement's of thereaction, or the properties of the finished product, any undesirable excess of anyojf the 1 ingredents; being removed by jetting or; extraction with suitable solvents, it being. understood that thiswremovaltaffectsz onlyitthet uncombined ingredients and does not diminish the acidity @dueto the presence of'partially esterifled-polybe desirable to preparea product which fconequivalent of resin. By equivalentfof resin" is meant theweight of reslnhaving the'esterlficationproductyof "1 molof the inner ether of the when thelatterproportions of acid are used in number sheared; the amountoi acid employed {basic acid residues. tFor 'most purpos espit willtains less than one and preferably lessthan' one half equivalent ofuncombined, acid" per,

, h 3 parent polyhydric alcohol therein; or wherejderivatives of more than one polyhydric alcohol are present in the resin, theequivalent of resin-is the weight of resin having; therein the esterification product of innerethers, the sum themol fractions of which is one, Thefact that. the e'sterificatlon reaction does not involve allthe normally esterifiable hydro xyl ligroups of the hexahydric "alcohol when that compound is employed as the initial reactant, and the fact thatju on sappnification of the esteri fication product, "the inner etherand not the hexahydric alcohol is recovered, show clearly that tinder. the conditions of esterificatijon, the

hexahydric alcohol undergoes an intramolecular condensation tcform an inner ether, which prod essflobviously reduces the number of ,hyd Y groups in theniolecule. by two for each oxido-ring formed. V a The esterification reactionmaybe carrled out in any suitable manner and, at any elevated temperature which results in the formation of resinous; 'esterlfied ihner ethers. The optimum temperature for the reaction will depend upon the reactivity of the organic acid qr, acids enlployed, and the 'mixture of the reactants is maintained at the elevated temperature untiljthe esterification is "substantially epmplete. The reaction will take place in "the absence of a catalyst, but ifit is ,desiredjtoreduce, the length of time required for the reaction, any of the usual fle steriflcation catalysts such as, boric anhydride I or zincidust may beused. We'havefound that the quality for the resin may bejl improved by carrying out the reaction inani'nert atmosphere, e. g.,\ in carbondioxide' orflnitroge'n. Furthermore, we have founditdesirable in certain cases to remove excess of volatile ingredients and .un-

desirable volatile lay-products formed during the reaction by letting with inertjgases suchas carbon dioxide" or nitrogen.

. ,Theprop erties of these resinous"esterificationproducts depend onthe natureand proportion of the'reactants, and'on the methodof preparation.

'Ifhus' the color, solubility; behavior, mechanical properties, chemical lstabillty, .etc;; maybe alterejd by using different polybafsic aoi'dsgj Malelc, a for example, gives very light, water-soluble ma terials; and phthalicgives productshavih'g higher solubility in hydrocarbon solvents. Merely "by varying the heating time,esters ran'gingin char acter from. soft, readily. soluble, highlyacid niarenal of low average molecular weight, to highly polymerized; hard, insoluble-, v-linfusible products may beobtained. In making esters of thistypr, the latter stagesof the reaction are rpreferably carried outby heating or curihg inovens. fI'hese resinous esters may be usedfeitherjalone, mixed with other, materials, and/ordissolved' in suit:

able solvents, foruseYin eoatingfcompositions,

impregnants, binders,f adhesives, insulating ma terial, molding composition. and the like. They may be rnixedfwith dryihghils in-the preparationname; A particularly wide application is-in the a cellulose Yderivatlve such as the nitrate; acetate, or ethyl or benzyl ether, agsolverit', a plasti- Since the resinous esters are heat hardening; theyare valuablein gradients in baking enamels'. other similar ap-' plications willoccur tofthose having acquaint- Where phthalicfacid'is one cry-the reactants, the properties otith'e resin may be modified by nformulation of lacquers, using there'sino'usester, I

the replacement of a portion of the polycarboxylic acid by a fat y oil acid, which term as used herein, includes the air-drying acids, and the long chain monobasic organic acids containing at least twelve carbon atoms and not more than one ethylene linkage.

If a resin of the air-drying type is desired, a portion of the polycarboxylic acid (which in the production of air-drying resins should comprise phthalic acid or anhydride, either aloneor in admixture with the resinifying, aliphatiopolycarboxylic acids set forth above) may be replaced with an air-drying acid. As examples of air-drying acids may be mentioned linoleic, linolenic, eleostearic acid, and other acids characterized by a plurality of double bonds and the property of drying by atmospheric oxidation. Such acids may be obtained synthetically or by saponification of the commondrying oils-such as linseed oil, perilla oil, China-wood oil, menhaden oil, and thelike. These acids may be employed in pure form, mixed, or containing small amounts of non-drying, aliphatic acids.

In the production of air-drying resins, the ratio of polycarboxylic'organic acid to air-drying acid employed in the process may vary widely, depending upon the properties desired in the resinous material. Thus, with a large proportion of air-drying acid and a small amount of poly carboxylic acid, a product is obtained which has properties clearly related to that of a drying oil. By increasing the polycarboxylic acid and decreasing the air-drying acid, the viscosity of the resinous product is increasediand its solubility is decreased until, with a very small amount of air-drying acid and a large amount of polycarboxylic acid, .an insoluble and infusiblc product is obtained. In the preparationof resins suitable for synthetic enamels, for instance, a

' satisfactory inol ratio of linseed oil acids to neighborhood of P age. The saturated acids, including those whose formulae may be represented by CnHZnOZ, where n is at least 12, for example lauric, myristic, palmitic, and stearic acids, as well as the unsaturated acids containing only one ethylene linkage, for exampleoleic and ricinoleic acids, fall within this class. These acids do not possess characteristic air-drying properties. Theymay be obtained synthetically or more conveniently by saponification of the natural oils, animal or vegetable, such as castor oil, coconut oil, olive oil, lard, tallow, soya bean oil, corn oil, cotton seed oil, and the like, the acids derived, from cottonseed oil being known as beta fat. The

monobasic acids contemplated herein may be used either pure or in the form of mixtures, which mixtures may contain small amounts of glycerides and more-unsaturated acids.

The ratio of resinlfying polycarboxylic organic acid to monobasic semior non-drying acid employed in the process may vary widely, depending on the properties desired in the resinous material; in a typical instance, the .m'ol ratio of the monobasic acid to polycarboxylic acid may be from .3 to .9. As the proportion of the monobasic acid is increased, the tendency to gelation and the viscosity in solution decrease while the solubility, the compatibility with oils, the softness, and the weathering resistance increase. By choosing suitable proportions of the 'polycarboxylic and monobasic acids, the properties of the product may thus be varied-from those of an almost insoluble and infusible resin to those of the nonor semi-drying oils.

It is knownthatin fatty oilacidodlfied glycerol base resins, .whose greatest usefulness lies in the field of coating compositions, the viscosity decreases as thefatty oil-acid content of the resin is increased. Coating compositions, particularly pigmented types, demand the use of resins having viscosities highenough to keep the pigment satisfactorily suspended during storage. This requirement sets an upper limit to the fatty oil-acid content of technically useful resins. A high drying acid content is, however, desirable, since it confers increased weather resistance and quicker and more extensive drying powers on the finished composition. Similarly,

high semior non-drying oil-acid content confers increased weather resistance in the finished composition. Furthermore, resins prepared from high semior nondrying oil-acid content reaction mixtures have the advantage of high solubility and cheaper solvents.

The use of polyhydroxy cyclic inner ethers in the preparation of fatty oil-modified resins greatly increases the viscosity in ordinary lacquer solvents, and thus permits the preparation of technically valuable resins of much higher fatty oil-acid content than has hitherto been disclosed. 1 I

The air-drying resins are particularly applicable in formulating synthetic enamels comprising the resin, a solvent, a pigment, and a slew.- tive, with or without a plasticizer. The semior'non-drying oil-modified type resins are particularly applicable in .the formulation of baking enamels comprising the resin, a solvent and a pigment, with or without a plasticizer. The fatty oil-modified type resins are also particularly usefulin the formulation of lacquers, and for this purpose, may be combined with plasticizers, coloring agents and cellulose derivatives of the type previously mentioned. They may also be used in paints, varnishes, binders, adhesives and impregnants with the usual ingredients. Other uses of the fatty oil-modified resinous materials, and the incorporation therewith of other materials, will naturally suggest themselves to those familiar with the field.

The following specific examples are given to illustrate the manner of carrying out my in.

vention and the character of the products derived therefrom.

Example 1 causing the mixture to melt. The molten mass is heated at the rate of 2 C. rise in five minutes until a temperature of 177 C. is reached. The rate of temperature rise is then ecreased to 1' C. in five minutes until a temperature of 218" C. is reached. The resulting product is 182 parts of dry-sorbitol and 148 parts of \phthalic anhydride are heated in an atmosphere of carbon dioxide and with stirring to 120 C., this ratio corresponding to 2 equivalents of acid per mol of ,hexahydric alcohol. The mixture is then heated in the course of an hour to 200 C. and heldat this temperature for four hours, whereupon it is cast. During this last heating period, the reaction mass is jetted with carbon dioxide. The resin is dark brown in color, has an acid number' of 43.4 and a softening point of 89.4 C. This resin is insoluble in ethylene dichloride and in ethyl and butyl acetate; partially soluble in acetone and toluol and soluble in a mixture of alcohol and toluol.

Example 3 91.0 parts of mannitol are intimately mixed with 98 parts of maleic anhydride, this ratio corresponding to 4 equivalents of acid per mol of hexahydric alcohol. 'The mixture is heated in an atmosphere of' carbon dioxide to a temperature of 130C. At this temperature, the mixture becomes molten and stirring is started. The temperature is raised gradually to 180 C. in 75 minutes, a stream of carbondioxide being passed into the reaction vessel during the heating period. At 180 C., gelatinization occurs. The

1 product on cooling is an almost colorless, hard,

vitreous mass, capable of softening on heating.

Example 4 93.2 parts of sorbitol syrup obtained from the reduction of glucose and containing 7.03% moisture are heated to C. in an atmosphere of carbon dioxide and 50 parts of maleic anhydride are stirred in, this ratio corresponding to approximately 2 equivalents of acid per mol of hexahydricalcohol. The temperature is raised to 150 C. in the course of an hour. During this time, the mixture is stirredi'n an atmosphere of carbon dioxide. The resinis cast. It is a clear, almost water white, hard mass, somewhat sticky, soluble in water, with an acid number of 177.

Example 101 parts of sorbitol syrup produced by the reduction of glucose and containing 7% moisture, 80.1 partsof succinic acid are introduced into a reaction vessel and mixed at a temperature of C., this ratio corresponding to about 2% equivalents of acid per mol of hexahydric alcohol. The temperature is then raised at airate of C. per minute until ,a temperature of 195 C. is reached. The product is dark in color,tough and rubbery when hot, and sets to a brittle mass at room temperature. 1

Example 6 210 parts of a sorbitol syrup prepared by the reduction of glucose and. containing 7% moisture are heated to C. and 168 parts of tar- ,taric. acid monohydrate are stirred inunder an atmosphere of carbon dioxide, this ratio corresponding to about 2 equivalents of acid per mol of hexahydric alcohol. 1 The temperature israised gradually, with stirring under an atmosphere of carbon dioxide, to a temperature of 160 C. in the course of two hours, at the end of which time foaming has ceased. The temperature is held at 160 C.for twenty minutes, at which The product is light brown in color.

' dioxide for four hours.

water, but is substantially insoluble in the usual organic solvents. Its softening point is 89.5 C.

Example 7 One mol of sorbitol and one mol of citric acid are heated to C. This ratio of sorbitol and citric acid corresponds to about 3 equivalents of acid per mol of the hexahydric alcohol. The mixture is stirred in an atmosphere of carbon dioxide during the heating. The temperature of-the reaction mixture is raised to 160 C. in the course of an hour. The heating is continued at 160 C. until the reaction mixture becomes too viscous to stir. This will require about one hour. It is soluble in water but is insoluble in the common organic solvents. i

i Erample 8 Onemol of sorbitol is heated to 80 C. and one mol of maleic anhydride is stirred in. The temperature is raised to 100 C. and one mol of phthalic anhydride is similarly added and stirred into the mixture. This amount of sorbitol and phthalic and maleic anhydride corresponds to about 4 equivalents of acid per mol of the hexahydric alcohol. The temperature of the mixture is then raised gradually. with stirring in an atmosphere of carbon dioxide to 195 C. in the course of three hours, at which point the resin gels. The resin is insoluble in the usual organic solvents. The resin, when heat is applied, will soften but will not melt without decomposition. It forms a dark brown vitreous mass when cold.

Example 9 To, one mol of sorbitol, stirred and heated in an atmosphere of carbon dioxide, 1.125 mols of phthalic anhydride are added at C. This ratio of acid to sorbitol corresponds to 2%, equivalents of'acid per mol of the hexahydric alcohol. Heating is continued at a temperature increase of 1 C. per minute until a temperature of 200 C. I

is reached. The reaction mixture is heated at this temperature in an atmosphere of carbon At the end of this time, the resinous product is cast in aluminum pans. 'I'heresin has a softening point of about C. It is sparingly soluble in a 50-50 mixture of alcohol and toluol and is insoluble in acetone, ethylene dichloride, toluol, butyl and ethyl acetate and I alcohol.

Example 10 To one mol of mannltol,-1.125 mols of malic acid (corresponding to 2.25 acid equivalents per mol of the hexahydric alcohol) are added. The mixture is heated in an aluminum reaction vessel in an inert atmosphere of carbon dioxide until a. temperature of C. is reached. Agitation is then started. Heating is continued so that the temperature rise is 1 C. per minute until a temperature of C. is reached. Heating is continued at this temperature for approximately seventy-five minutes longer. The reaction mixture will then tend to solidify. The resinous reaction mixture is insoluble in the ordinary organic solvents. It is also infusible.

Example 11 To one mol of mannitol, 1.125 mols of phthalic anhydride (corresponding. to 2.25 acid equivalents per mol of the hexahydric alcohol) are added. The mixture is heated in an aluminum reaction vessel in an atmosphere of carbon dioxide until the solids melt. Agitation is then started. Heating is continued so that the temperature rise will be 1 C. per minute. When a temperature of 200 C. is reached the reaction mixture is held at this temperature for 4 hours longer, the mixture being stirred in an atmosphere of carbon dioxide. The resinous product is then cast in aluminum pans. It has a softening point of about 106 C. It is soluble in warm acetone, partially soluble in a 50-50 solution of alcohol and toluol, and insoluble in butyl and ethyl acetates, ethylene dichloride, alcohol and toluol.

Example 12 To one mol of sorbitol, .281 mol of maleic anhydride and .844 mol of phthalic anhydride (corresponding to 2.25 acid equivalents per mol of the hexahydric alcohol) are added. The mixture is heated to a temperature of C. in an atmosphere of carbon dioxide. At this temperature, the reaction mixture begins to melt and stirring is started. Heating is continued so that the temperature rise will be 1 C. per minute until a temperature of 200 C. is reached. The reaction mixture is heated at 200 C. for four hours, the mixture being agitated in an atmosphere of carbon dioxide during this heating period. At the end of this time, the resinous product is cast in aluminum pans. It has a softening point of approximately C. It is sparingly soluble in a 50-50 mixture of alcohol and toluol and insoluble in acetone, ethylene dichloride, toluol, alcohol and butyl and ethyl acetates.

Example 13 One mol of sorbitol and 0.625 mol of linseed oil acid are introduced into an aluminum reaction vessel. The mixture is stirred and heated to a temperature of 120 C. 0.81 mol of phthalic anhydride is added. After these ingredients are added, the temperature is raised uniformly to 200 C. in 100 minutes. The heating is continued at 200 C. for 3 hours. The incorporation and reaction of ingredients is at all times carried out in an atmosphere of carbon dioxide. The heating is stopped and the reaction mixture is cooled to 150 C. under carbon dioxide. At this temperature, the resin is run into aluminum receptacles.

The resin is soluble in V. M. 8: P. naphtha, toluol, benzol, butyl alcohol, acetone, ethyl and butyl acetate, and cellosolve. When exposed to the action of the air in thin layers such as those obtained by the evaporation of solutions in volatile solvents, the resin dries to a hard, tough, insoluble film. The drying action is accelerated by the addition oi siccatives. The viscosityof a 65% solution of this resin in c. p. toluol at 25 C. is about 6.2 poises.

Example 14 One mol of sorbitol and 0.64 mol of linoleic acid are heated as in the foregoing example, 0.804 mol of phthalic anhydride is added and the heating continued as there described.

The resin is soluble in V. M. & P. naphtha, toluol, benzol, butyl alcohol, acetone, ethyl and butyl acetate and cellosolve. The resin has drying properties similar to those of the resin de scribed in Example 13.

The viscosity of a 65% solution of this resin in 0. p. toluol at 25 C. is about 5.6 poises. The molar ratio of linseed oil acid to phthalic anhydride was 0.80.

Example 15 One mol of sorbitol and 0.625 mol of linseed oil acid are heated as described in Example 13. 0.66 mol of phthalic anhydride and 0.14 mol of maleic anhydride are added. The mixture is heated to 200 C. as in Example 13. After a temperature of 200 C. is reached, heating is continued for four hours.

The finished resin is soluble in V. M. 8: P. naphtha, toluol, benzol, acetone, butyl alcohol, ethyl and butyl acetate, and cellosolve.

The viscosity of a 50% solution of this resin in c. p. toluol is approximately 3.6 poises at 25 0.

Example 16 One mol of sorbitol and 0.625 mol of linseed oil acid are heated as described in Example 13. 0.54 mol of phthalic anhydride and 0.274 mol of adipic are added. The mixture is heated as in Example 13.

The finished resin is soluble in V. M. 8: P.

naphtha, toluol, benzol, acetone, butyl alcohol, ethyl and butyl acetate, and cellosolve.

The viscosity of a 65% solution of this resin in c. p. toluol is about 11.5 poises at 25 C? Example 17 Example 18 0.5 mol of linseed oil acid and 0.75 mol of phthalic anhydride are heated together to a temperature of C. with stirring. 1 mol of mannitol is added and heating continued so that the temperature is raised at the rate of 1 C. per minute until a temperature of 200 C. is reached. The heating is continued for 4 hours at this temperature. All mixing and reaction of ingredients are caried out in an atmosphere of carbon dioxide.

The finished resin is soluble in V. M. 8: P. r

naphtha, soluble in toluol, benzol, acetone, and butyl and ethyl acetate. The viscosity of a 65% solution of this resin in c. p. toluol is about 32 poises at 25 C.

Example 19 182 parts sorbitol and 80 parts beta fat (cottonseed fatty acids) are introduced into an aluminum reaction vessel. The mixture is stirred and heated to 120 C. parts of phthalic anhydride are added. After these ingredients are added, the temperature is raised uniformly at a rate of 1 C. rise per minute until a temperature of 200 C. is reached. The heating is continued at 200 C. for three hours. The incorporation and reaction of ingredients are at all times caried out in an atmosphere of carbon dioxide. The heating is stopped and the reaction mixture is cooled to C. under carbon dioxide. At this temperature, the resin is run into aluminum receptacles.

The resin is soluble in alcohol, ethyl and butyl acetates and acetone. It is partly soluble in toluol and ethylene dichloride and insoluble in V. M. a P. naphtha. It has a softening point of bout 78 on The viscosity of a 65% solution in butyl acetatei s about 38 poises at 25 C.

. phth'alic anhydride areadded-iand :the heating is continued as inlExample 19. 1 U

mg is continued as m Exam le 19.

' & P.naphtha'. I v 1 1 I The viscosity of. a 65 solution in l'outylac'etate phthalic anhydrid'e are jadde continued. as in Example .19.

-,'I he resin is soluble in alcohol, ethylene dichloride, acetone andjbut'yl and ethyl ac'etatesi It is slightly soluble in toluol anddnsolublein-V. M. I & P. naphtha; 65% solution ofthe' resin in; butyl acetatehas' a viscosity of about l2 'poises ig at25 C..

l ammbzzz I "182 parts ofsorb'itol andl65 partsof1beta fat.

I I "are heated as in Example 19lf ..l25 parts' off phthali'c anhydride are added andthe heatingisfl continuedas in Example 19.

"s partly solublein toluol and in soluble in 'V.

is about 3.1 poisesat 25" c.

Example 22 91 parts of sorbitol and 145 parts ofstearic acid 110iparts of mi heating is are heated as in-Example;

1 The resin is soluble in} acetone, 1 butyl and ethyl acetates, ethylene dichloridejV. & P. naphtha-, I

alcohol. and: toluoL A 65% 'solution'of the resin 1 in butyl acetate hasaviscosityof about 1.1 poises.at,25 C.f

l l rmampze zs 182 parts of SOl'bltOl and 112 parts of coconut resin butyl acetate has a viscosity of approx t mately 7 2 poises at 25 C. 1 f l Considerable modification is possible in the choice of the ingredients employed in the esterifi- 'cationreaction as'well asin the manipulative *step's utilized. in the processes, without departing from thees'sential features of theinvention.

oilj 'aclds are-heated as" in Example 19'.- 1 18.5 parts of phthalic anhydride are added he resin is solubleli butyl andwethyl"acetateslj acetone-,alcohol. and ethyleneidichloride; It is insoluble in V." Mi tzgP-anaphthafi andpartly sol ubl'e inl'toluol. 6 solutionof the-resin in butyl acetate has afviscositypf about 5.1 poises, at 25 I I I j amamplefzrfl 182 parts ofs'orbitollandf parts 01 corn oil acids are heated as in Example 19. 148 parts of phthalic'anhydri'de are added and heating is' continued as, inEX'ample 19.

I The resin is soluble in acetone,alc0hol, ethylene dichloride, and butyl and ethyl acetates;

It is partly solublein toluolYandV. M." & P. naphtha. -A 65% 'solutionlof this resin inbutyl acetate'hasa viscosityof. about 2.4 poises at 25 C. c0

. 182 parts 0f sor'bitol and'I O parts"of -oleic acid are heated as in="Exampl e-'19. 148 parts of It is slightly soluble intoluol and 1.6 poises at 25 C.

7 -E:cample 26 1 182 parts of sorbitoland 175 partsofricinoleic 1 "acid are heated as .in Example 194 120 parts mate'ly 3.1 poises at 25 C.

out in an atmosphere of carbon dioxide. "reaction mixture is cooled to 150 C. under carbon dioxide, atwhich temperature the resin is run" into aluminum receptacles.

The'resin issoluble in a'cetonef alcohol; and butyl and ethyl acetates. 1 *ene"dich1oride, V. M. &P. naphtha and toluol.

A 65 solution of-this resinin' butyl acetate I The resin is soluble in acetone; alcohol; ethyl-"6 ene dichloride' and butyl andethyl acetates. It

of phthalic anhydride 1 are 'addedand the-heating 'is continued as in,-Example 19. 1

a liThe' resin =is soluble in"-alcohol; acetone 'and I I I I I I I 1 ethyl-g'and"butyl'jacetates.- It is partly soluble 1 182 parts of s'orbitol andlzfi parts o-beta fatb are heated as in" ExampIe 19'. 133: parts 1 of in toluol, and insoluble in ethylene dichloride and V. M-. -& P-gnaphtha. A 65% solution of-this resinin butyl acetate has a viscosity of approxi- 138.5 parts of phthalic anhydride and105 parts oleic acid are heated together-in an aluminum All mixing'and reaction of ingredients are carried The It is insoluble in ethylhas a-viscosity of approximately 6;? poises at 25" c.

' 1 Example 28 I fss- -partsror phthalic anhydride and 88.5 parts v.of palmitic acid are heated as in Example 27. ,91 partsof mannitol are added and the heatin is continued as in Example 27. 1

Theresin is soluble in acetone, ethylene di- 1 chlorideand butyl and ethyl acetates. It is part- 1 ly soluble in toluol' and insoluble in V. M. 8; P.

naphtha and alcohol. A 65% solution of-this W1'iatIclaim is: 1 Q

1'. Thewprocess of makinga resinous material 1 'comprising an. esterification product-of an inner ether; which comprisesheating together under esterifyin'g conditions .resinifying polycarboxylic aoidysaid acid comprising phthalic acid when iatt'y oil acid is present in the reacting, mixture. andapolyhydroxyinner ether derivable from a straightchain hexahydrio alcohol by intrarnol'ecular condensation thereof, the number of equivalents of acid present in the reacting mixture being not more than about 4 equivalents Der mol of ether. 1 I l l I 2. The process of makingaresinous material comprising an esterification product'of an inner ether "which comprises heating together under esterifying conditions phthalic acid and a polyhydroxy inner ether derivable from a straight chain hexahydric alcohol by intramolecularcondensation thereof, the number of equivalents of acid present in thereacting mixture being. not 'more than about iequivalents per molof ether.

3.--The process of making a resinous material comprising an esterification product of an inner ether which co'mprises heating together under esterifying conditions phthalic acid and a poly- 'hydroxy inner ether derivable from a straight chainhexahydric' alcohol by intramolecular condensation thereof, the number of equivalents 01 acid present in the reacting mixture being from 2.25 to 3 equivalents per mol of ether.

4. The process of making a resinous material comprising an esterification product of an inner ether which comprises heating together under esterifying conditions phthalic acid, a resinifying aliphatic polybasic acid, and a polyhydroxy inner ether derivable from a straight chain hexahydric alcohol by intramolecular condensation thereof, the number of equivalents of acid present in the reacting mixture being not more than about 4 equivalents per mol ofether.

5. The process of making a resinous material comprising an esterification product of an inner ether which comprises heating together under esterifying conditions phthalic acid, a resinifying aliphatic polybasic acid, and a polyhydroxy inner ether derivable from a straight chain hexahydric alcohol by intramolecular condensation thereof, the number of equivalents of acid present in the reacting mixture being from 2.25 to 3 equivalents per mol of ether.

6. The process of making a resinous material comprising an esterification product of an inner ether which comprises heating together under esterifying conditions phthalic acid, a resinifying aliphatic polybasic acid, fatty oil acid, and a polyhydroxy inner ether derivable from a straight chain hexahydric alcohol by intramolecular condensation thereof, the number of equivalents of acid present in the reacting mixture being not more than about 4 equivalents per mol of ether.

'7. The process of making a resinous material having air-drying properties and comprising an esterification product of an inner ether which comprises heating together under esterifying conditions phthalic acid, a resinifying aliphatic polybasic acid, an air-drying acid, and a polyhydroxy inner ether derivable from a straight chain hexahydric alcohol by intramolecular condensation thereof, the number of equivalents of acid present in the reacting mixture being not more than about 4 equivalents per mol of ether.

8. The process of making a resinous material having air-drying properties and comprising an esterification product of an inner ether, which comprises heating together under esterifying conditions phthalic acid, maleic acid, an air-drying acid, and a polyhydroxy inner ether derivable from a straight chain hexahydric alcohol by intramolecular condensation thereof, the number of equivalents of acid present in the reacting mixture being not'more than about 4 equivalents per mol of ether.

9. The process of making a resinous material comprising an esterification product of an inner ether which comprises heating together under esterifying conditions resinifying aliphatic polybasic organic acid and a polyhydroxy inner ether derivable from a straight chain hexahydric alcohol by intramolecular condensation thereof, the number of equivalents of acid present in the re- .acting mixture being not more than about 4 equivalents per mol of ether.

10. The process of making a resinous material comprising an esterification product of an inner ether which comprises heating together under esterifyingconditions resinifying aliphatic polybasic organic acid and a polyhydroxy inner ether derivable from a straight chain hexahydric alcohol by intramolecular condensation thereof, the number of equivalents of acid present in the reacting mixture being from 2.25 to 3 equivalents per mol of ether.

11. The process of making a resinous material comprising an esterification product of an inner ether which comprises heating together under esterifying conditions maleic acid anda polyhydroxy inner ether derivable from a straight chain hexahydric alcohol by intramolecular condensation thereof,'the number of equivalents of acid presentv in the reacting mixture being not more thanabout 4 equivalents per mol of ether.

12. The process of making a resinous material comprising an esterification product of an inner ether which comprises heating together under esterifying conditions phthalic acid, maleic acid and a polyhydroxy inner ether derivable from a straight chain hexahydric alcohol by intramolecular condensation thereof, the number of equivalents of acid present in the reacting mixture being not more than about 4 equivalents per mol of ether.

13. The process of making a resinous material comprising an esterification product of an inner ether, which comprises heating together under esterifying conditions phthalic acid, fatty oil acid, and a polyhydroxy inner ether derivable from a straight chain hexahydric alcohol by intramolecular condensation thereof, the number of equivalents of acid present in the reacting mixture being not more than about 4 equivalents per mol ditions phthalic acid, an air-drying acid and a polyhydroxy inner ether derivable from a straight chain hexahydric alcoholby intramolecular condensation thereof, the number of equivalents of acid present in the reacting mixture being not more than about 4 equivalents per mol of ether.

16. The process of making a resinous material having air-drying properties and comprising an esterification product of an inner ether which comprises heating together under esterifying conditions phthalic acid, an air-drying acid, and a polyhydroxy inner ether derivable from a straight chain hexahydric alcohol by intramolecular condensation thereof, the number of equivalents of acid presentin the reacting mixture being from 2.25 to 3 equivalents per mol of ether.

17 The resinous esterification product made in accordance with the process set forth in claim 1.

18. The resinous esterification product made in accordance with the process set forth in claim 2. 19. The resinous esterification product made in accordance with the process set forth in claim 3. 20. The resinous esterification product made in accordance with the process set forth in claim 9. 21. The resinous esterification product made in accordance with the process set forth in claim KENNETH R. BROWN. 

